J Soils Sediments (2013) 13:152–165
DOI 10.1007/s11368-012-0599-5
SOILS, SEC 4 & ECOTOXICOLOGY & RESEARCH ARTICLE
Remediation of a diesel-contaminated soil from a pipeline
accidental spill: enhanced biodegradation and soil washing
processes using natural gums and surfactants
Antonio Hernández-Espriú & Emilio Sánchez-León &
Pedro Martínez-Santos & Luis G. Torres
Received: 2 November 2011 / Accepted: 31 August 2012 / Published online: 15 September 2012
# Springer-Verlag 2012
Abstract
Purpose This paper addresses the application of bioprod-
ucts produced by plants (locust bean, guar, and mesquite
seed gums) to enhance remediation processes of different
nature: soil washing and biodegradation methodologies.
Materials and methods These natural gums were tested at
laboratory scale to remove total petroleum hydrocarbons-
diesel fraction (TPH-diesel) from oil-contaminated volcanic
soils sampled from a polluted site in an agricultural area of
western Mexico. TPH-diesel removal by natural gums was
compared to common synthetic surfactants.
Results and discussion There is a strong evidence of con-
tamination caused by the presence of TPH-diesel at a con-
centration of 32,100 mg/kg, which is above the legal limit of
1,200 mg/kg for agricultural soils in Mexico. Regarding the
surfactant soil washing experiments, ionic surfactants
showed removal rates above the control test of about
78.51 % (Maranil LAB), 71.27 % (Texapon 40), 60.13 %
(SDS), and 48.19 % (Surfacpol G). In contrast, some non-
ionic surfactants showed removal rates below soil-washing
Responsible editor: Qixing Zhou
A. Hernández-Espriú (*) : E. Sánchez-León
Hydrogeology Group, Earth Sciences Division, Faculty of
Engineering, Universidad Nacional Autónoma de México,
Ciudad Universitaria,
México City 04510, Mexico
e-mail: ahespriu@dictfi.unam.mx
P. Martínez-Santos
Department of Geodynamics, Faculty of Geological Sciences,
Universidad Complutense de Madrid,
C/José Antonio Novais 2, Ciudad Universitaria,
28040 Madrid, Spain
L. G. Torres
Department of Bioprocess, UPIBI, Instituto Politécnico Nacional,
Av. Acueducto S/N Col, Barrio La Laguna Ticomán,
97340 México City, Mexico
background rate (40 %). On the other hand, natural gums
showed interesting and promising results. Guar gum and
locust bean gum showed efficiencies of 54.38 % and
53.46 %, respectively. Biodegradation experiments con-
firmed the effectiveness of natural gums as biodegradation
enhancers in diesel-contaminated soils. Specifically, guar
gum showed an excellent performance. An 82 % TPH-
diesel removal rate was achieved for a very low gum con-
centration (2 ppm). In this particular context, reported sur-
factant concentrations to assist biodegradation are, in
general, higher.
Conclusions This work demonstrated the applicability of
natural gums as soil remediation enhancers in diesel-
contaminated systems. Particularly, guar gum might repre-
sent a cost-effective alternative for biodegradation enhance-
ment processes.
Keywords Enhanced remediation . Guar gum . Natural
gums . Soil remediation . Surfactants
1 Introduction
There are many ways in which diesel can reach the vadose
zone, thus contaminating soils and aquifers. Particularly in
oil-based economies, leakage from pipelines due to instal-
lation failure or even to burglary activities can represent an
important environmental threat. Other circumstances which
produce diesel-contaminated soil are accidental spills from
vehicles or leaks in storage tanks. Take for instance the case
of Mexico. This country presents a strong oil industry,
comprehending all stages of the manufacturing process:
exploration, production, transformation, storage, and distri-
bution of crude oil and its fractions. Over 30 % of the
pipeline systems, which transport crude oil and subproducts
all around the country, have been operating for over 30 years
J Soils Sediments (2013) 13:152–165
when their lifetime has been calculated in 25–30 years
(Iturbe et al. 2007).
Thus, cost-effective remediation systems are of para-
mount importance to deal with oil contamination in soils
and aquifers. Different remediation methodologies have
been reported to minimize diesel contamination. These in-
clude electro-remediation of contaminated soils (Page and
Page 2002), ozonation (Goi et al. 2006), solidification/sta-
bilization (Knop et al. 2005), and the application of Fenton’s
reagent (Xu et al. 2006). Regarding the biological process,
methods such as treatment of diesel fuel contaminated soils
by jet-fluidized bed (Arrar et al. 2007), bioventing and
composting (Mao and Yue 2010), biostimulation (Mariano
et al. 2007; Sharma and Rehman 2009), and in situ biore-
mediation (Liu et al. 2008) have also been applied.
The use of surfactants to enhance conventional remedia-
tion techniques, such as soil washing and biodegradation
processes, is also well documented (Mulligan et al. 2001;
Torres et al. 2003; López et al. 2004; Vreysen and Maes
2005; Zhou and Zhu 2007, 2008; Khalladi et al. 2009;
Zhang and Zhu 2010). In particular, biosurfactants originat-
ed by yeast or bacteria from various substracts including
sugars, oils, alkanes, and wastes (Mulligan et al. 2001) have
prevailed as interesting remediation solutions. Desirable
surfactant characteristics include biodegradability, low tox-
icity, solubility at groundwater temperatures, low adsorption
to soil, and effectiveness at concentrations below 3 %. Lai et
al. (2009) reported oil removal capability of two biosurfac-
tants for TPH-contaminated soils from an oil refinery plant
in southern Taiwan. They used rhamnolipids produced by
Pseudomonas aeruginosa and surfactin produced by Bacil-
lus subtilis, as well as synthesized surfactants, such as
Tween 80 and Triton X-100. According to these authors,
rhamnolipids and surfactin showed superior performance on
TPH removal from both slightly (3,000 mg/kg) and high
(9,000 mg/kg) TPH concentration in soils. Other research
studies where rhamnolipids and surfactin, and even other
biosurfactants such as humic acid, were employed as natural
enhancers can be found in Whang et al. (2008) and Conte et
al. (2005), respectively.
On the other hand, bioproducts produced by plants
(gums) have received lesser attention as natural remediation
agents. Natural gums are extensively used in a variety of
industrial applications due to their emulsifying, microencap-
sulating, thickening, and stabilizing properties (Orozco-Vil-
lafuerte et al. 2003; Román-Guerrero et al. 2009). Available
studies refer mostly to the use of lecithin (Soeder et al. 1996;
Urum and Pekdemir 2004), aescin, saponin, and tannin
(Urum and Pekdemir 2004).
This research evaluates the potential of three different
gums as soil-remediation enhancers: (1) locust bean gum
(LBG), a white-yellowish powder found in Mediterranean
regions and obtained by crushing the endosperm of seeds
153
from the fruit pod of the carob tree (Ceratonia siliquia L.)
(Dakia et al. 2008); (2) guar gum, from the galactomannans
family, which consists of a (1–4)-linked β-D-mannopyra-
nose backbone with branch points from their 6-positions
linked to a D-galactose (Chaplin 2003); and (3) mesquite
seed gum, a natural polysaccharide exuded by the bark of
Prosopis spp trees (Román-Guerrero et al. 2009). This sub-
stance is one of the main natural resources and common
cultural denominators for the inhabitants of desert regions in
southern USA and Mexico since Pre-Columbian times
(Orozco-Villafuerte et al. 2003).
In previous works, LBG and guar gum have been used to
remove TPH-diesel, TPH-gasoline, and heavier fractions in
soils of different nature with both successful (Torres et al.
2007) and unsuccessful results (Torres et al. 2004).
More specifically, this paper addresses the application of
LBG, guar, and mesquite seed gum to enhance remediation
processes of different nature: soil washing and biodegrada-
tion methodologies. These natural gums were used at labo-
ratory scale to remove TPH-diesel fraction from oil-
contaminated volcanic soils sampled from a polluted site
in an agricultural area of western Mexico. TPH-diesel re-
moval by natural gums is then compared to common syn-
thetic surfactants (SDS, Brij 35, and Tween 80 among
others).
2 Materials and methods
This section describes the experimental design, analytical
procedures, and materials of this research. It refers to diesel-
contaminated soil characterization, surfactants/natural
gums, and surfactant-enhanced biodegradation/soil-washing
processes at laboratory level (treatability tests). The concep-
tual framework is shown in Fig. 1.
2.1 Soil sampling and characterization
Soil samples were obtained at a contaminated site affected
by a diesel spill. Contamination stems from pipeline leaks
located at the western part of Trans-Mexican Volcanic Belt
geological province. The polluted vadose zone, previously
characterized at a field level (Hernández-Espriú 2010), com-
posed by quaternary non-consolidated volcanic ash depos-
its, was sampled at variable depths of 0.5 to 1 m in an area
of 75×12 m. During soil sampling, an AMS regular 4″ hand
auger was used following standard procedures (ASTM
2000) in order to get a mixed but representative sample for
further analysis.
Soil characterization included the evaluation of physical,
chemical, and microbiological properties (Table 1). Other
measured parameters were grain-size distribution, porosity,
nutrient concentration, metal content, microbial growth, and
154 J Soils Sediments (2013) 13:152–165

START

Contaminated Site

Soil Sampling at a field level

Soil characterization

Is initial
TPH-diesel concentration
known?
Are physical, chemical NO
and biological properties
determined?
(see Table 1)

YES

Treatability studies
at laboratory level

Enhanced soil-washing Enhanced biodegradation

experimental design experimental design

Soil-washing remediation test Microcosm assessment

with soil at TPH-diesel with soil at TPH-diesel
of 32,100 mg/kg of 32,100 mg/kg

Ionic surfactant at Natural gums at

6 ionic surfactants 3 natural gums 2, 20, 200 mg/kg 2, 20, 200 mg/kg

6 Nonionic surfactants No surfactant

control test Nonionic surfactant at No surfactant
1 zwitterionic surfactant 2, 20, 200 mg/kg control test

Zwitterionic surfactant at Sterilized control

2, 20, 200 mg/kg test

24 hours of rotational agitation 12 weeks of biodegradation process

and 1 hour of sedimentation (incubation)

Final TPH-diesel Final TPH-diesel Measure of parameters in

Measure of parameters in concentration biodegradated soil
concentration
washed soil Humidity
Humidity
Microbial growth
TPH and enhanced-TPH TPH and enhanced-TPH
removal rate Soil-washing Biodegradation process removal rate
estimation process discussion discussion estimation

Comparison between
the two surfactant-enhanced
remediation processes

Conclusions
Soil sampling and characterization/
Further analysis
END Soil washing remediation process

Biodegradation remediation process

Fig. 1 Conceptual framework showing the methodology employed in this research

J Soils Sediments (2013) 13:152–165 155

Table 1 Physical, chemical, and

microbiological properties of the Parameter Method/reference Value Unit
contaminated soil
Physical properties
Bulk density Nucleus method; Blake and Hartage (1986) 1.58 g/cm3
Real density Pycnometer method; ibidem 2.7 g/cm3
Total porosity Densities ratio; Danielson and Sutherland (1986) 41.6 %
Grain-size distribution
Gravel Screens; Juárez-Badillo and Rico (1973) 13 %
Sand 67 %
Fine fraction 20 %
Humidity Gravimetric method; NOM-021-SEMARNAT-2000 7.63 %
Field capacity Klute (1986) 25.9 % %
Adsorption coefficient Isotherms adsorption experiments (Torres et al. 2003) 2.86 L/kg
Chemical properties
TPH-diesel Soxhlet extraction (EPA3540C) 32,100 mg/kg
Organic content Walkley and Black (1934) 6.46 %
Organic carbon Ibidem 3.73 %
Nitrogen Micro-Kjeldahl method (NOM-021-SEMARNAT-2000) 391.43 mg/kg
Soluble phosphorus Bray and Kutz (1945) 7.38 mg/kg
Total phosphates NOM-021-SEMARNAT-2000 598.74 mg/kg
Cobalt NOM-147-SEMARNAT-2004 34.73 mg/kg
Manganese NOM-147-SEMARNAT-2004 190.12 mg/kg
Copper NOM-147-SEMARNAT-2004 102.83 mg/kg
Lead NOM-147-SEMARNAT-2004 14.53 mg/kg
Cationic interchange NOM-021-SEMARNAT-2000 51.38 mEq/100 g
capacity
pH Potentiometer method, field measurement 5.42 pH units
Microbiological properties
Microbial growth Plate dilution, Fernández et al. (2006) 2×1011 FCU/g soil

adsorption coefficient (Kd). Characterization results revealed
heavy TPH-diesel contamination. Therefore, it was deemed
appropriate to target this parameter during surfactant-
enhanced remediation processes.
In order to determine Kd, batch sorption isotherm experi-
ments were run, equilibrating aqueous solutions of diesel
with soil from the site (Torres et al. 2003). Soil samples
from a non-contaminated zone of the study area, with the
same lithology and physical properties of the polluted zone,
were prepared with a diesel sample extracted from the
subsurface of the site (Hernández-Espriú 2010; Hernández-
Espriú et al. 2012). Diesel was sampled with a bailer from a
3-in. PVC monitoring well. Six 20-g non-contaminated soil
samples were mixed with the extracted diesel to obtain
different concentrations of 3,000, 6,000, 9,000, 12,000,
and 15,000 mg/kg of TPH-diesel. Also, a control test was
performed on clean soil. Soil samples were equilibrated
under isothermal conditions for 48 h and were continuously
agitated using a SEV (INO-650MG10) shaker at 50 rpm.
The supernatant was discharged and final TPH-diesel con-
centration in soil (sorbed concentration) was measured in all
samples.
2.2 Surfactants and gums
Sixteen surfactants and biosurfactants (natural gums) were
used in this research: SDS, Maranil LAB, Polafix LO, Sur-
facpol 14104, Texaponn-40, Surfacpol G (ionic surfactants),
Emulgin 600, Brij 35, Canarcel 20, Tween 80, Surfacpol 203
(nonionic surfactants), Polafix CAPB (zwitterionic surfac-
tant), locust bean gum, guar gum, and mesquite seed gum
(galactomannan that works as biosurfactants). Some surfac-
tant features, such as chemical formulae, critical micellar
concentration, and hydrophilic–lipophilic balance, are shown
in Table 2. G/M represents the galacturonic/manuronic rate,
which is typical for every galactomannan.
Before soil washing tests, solutions were prepared in order
to improve dissolution of gums into distilled water. Surfactant
and gum concentrations were at a uniform dose of 0.5 %.
Tween 80 was also tested at 1 %. All natural gums were tested
at 0.5 % and mesquite gum at 0.1 %. This is because higher
gum concentrations showed high viscosities and caused diffi-
culties in soil-washing processes (Torres et al. 2007).
During biodegradation assessments, the following surfac-
tants and gums were tested at three different concentrations
156 J Soils Sediments (2013) 13:152–165

Table 2 Some properties of the surfactants and natural gums employed in this research

Name Chemical name Chemical formulae Ionic nature Molecular CMC (mg/L) HLB
weight

SDSa,b Sodium dodecyl sulfate C12H25NaO4S Anionic 288 400 40

Maranil Laba Sodium dodecyl C18H29NaO3S Anionic NR 1,392 NR
benzene-sulfonate
Polafix LO NR NR Anionic NR NR NR
Surfacpol 14104 NR NR Anionic NR NR NR
Texapon 40a Sodium lauryl ether sulfate CH3(CH2)10CH2 Ionic 440 1,458 NR
(OCH2CH2)nOSO3Na
Surfacpol G NR NR Ionic NR NR NR
Emulgin 600a Ethoxylated nonylphenol C9H19C6H4(OCH2CH2)nOH Nonionic NR 45 11
Poe 0 6
Brij 35a Ethoxylated lauryl-ether (CH2)10CH2(OCH2CH2)nOH Nonionic 1,119.5 39.6 16.9
Canarcel 20 Sorbitan monoleate C24H46CH6 Nonionic NR NR 8.6
Tween 80 Ethoxylated sorbitan C24H44O6 Nonionic 1,308 65.4 15
monoleate Poe0
Surfacpol 203 Ethoxylated nonylphenol C9H19C6H4(OCH2CH2)nOH Nonionic 483 NR 11
Poe 0 20
Polafix CAPBa Propylcocoamide betaine C19H38N2O3 Zwitterionic 342.5 100 NR
Mesquite seed gum Galactomannan G/M 0 1:1 NR Nonionic NR NR NR
Locust bean gum Galactomannan G/M 0 1:4 NR Nonionic NR NR NR
Guar gum Galactomannan G/M 0 1:2 NR Nonionic NR NR NR

NR not reported, CMC critical micellar concentration, HLB hydrophilic–lipophilic balance, G/M galacturonic/manuronic rate
a
Torres et al. (2007)
b
Torres et al. (2003)

(2, 20, and 200 mg surfactant/kg soil): Brij 35, Maranil
LAB, Polafix CAPB, guar, and locust bean gum.
2.3 Surfactant-enhanced washing process test
As per the procedure described by Torres et al. (2003), 6 g of
contaminated soil was put into 17 vials, and 30 mL of fixed
concentrations of surfactant solution were added (0.1 %,
0.5 %, and 1 %). A control test was performed by mixing
six grams of soil with 30 mL of distilled water. In this case,
no surfactant was added in order to compare the removal
efficiency of a conventional washing-soil methodology with
the surfactant-enhanced remediation process. Flasks were
kept at 28 °C (which is the annual mean temperature at site)
during 24 h in rotational agitation, using a SEV (INO-
650MG10) shaker, at 150 rpm. Flasks were opened ensu-
ingly. Soil was then sedimented and final TPH-diesel con-
centration was measured using a Soxhlet extraction method
(U.S. EPA 1996).
2.4 Surfactant-enhanced biodegradation test: microcosm
assessments
Following the procedures by Althoff et al. (2001), Tiehm and
Schulze (2003), and Torres et al. (2004), 17 wide mouth glass
flasks (microcosms) were used to store 30 g of contaminated
soil. It has been reported that optimum nutrient ratio in soil (C/
N/P) for biodegradation processes is in the order of 100:15–
10:1 (U.S. EPA 1995; Fahnestock et al. 1998; Torres et al.
2005). However, soil samples had nutrient ratios C:N:P of
100:1.2:0.02 (see Table 1). Hence, samples were conditioned
by adding a solution of 2.1 g of (NH4)2SO4 and distilled water
in every microcosm in order to offset nitrogen deficit in soil.
Natural concentration of P was kept to evaluate biodegrada-
tion and enhanced-biodegradation capability of the system for
a nutrient ratio of 100:15:0.02.
The experiment was carried out by adding surfactants at
concentrations of 2, 20, and 200 mg/kg to the soil of about
32,100 mg/kg TPH-diesel concentration (Table 3). This
served the purpose of evaluating the effect of the surfactant
dose in the biodegradation process. The underlying assump-
tion is that even low surfactant concentrations (e.g., 2 mg/
kg) can be enough to enhance, significantly, natural biodeg-
radation rates (Torres et al. 2004).
The desired amount of surfactant solutions and the water
necessary to maintain 20 % humidity were added (Torres et al.
2005). Then, soil was carefully mixed and flasks tightly closed
in order to assure no air exchange. Additionally, two control
tests were run. The first one (microcosm B16) was a sterile
blank, sterilized at 121 °C for 15 min in the laboratory. The
second one (microcosm B17) was the conditioned soil with a
nutrient ratio of 100:15:0.02. No surfactant was added in
J Soils Sediments (2013) 13:152–165 157

Table 3 Experimental design for the microcosm assessments

Microcosm Soil weight (g) Surfactant/dose (mg/kg) Surfactant type Surfactant solution added (μL) Distilled water added (μL)

B01 30.01 Brij 35/2 Nonionic 12 1,118

B02 30.01 Brij 35/20 120 1,080
B03 30.00 Brij 35/200 1200 0
B04 30.07 Maranil LAB/2 Ionic 12 1,118
B05 30.01 Maranil LAB/20 120 1,080
B06 30.00 Maranil LAB/200 1200 0
B07 30.03 Polafix CAPB/2 Zwitterionic 12 1,118
B08 30.05 Polafix CAPB/20 120 1,080
B09 30.07 Polafix CAPB/200 1200 0
B10 30.00 Guar/2 Natural gums 12 1,118
B11 30.05 Guar/20 120 1,080
B12 30.05 Guar/200 1200 0
B13 30.02 Locust bean/2 12 1,118
B14 30.05 Locust bean/20 120 1,080
B15 30.02 Locust bean/200 1,200 0
B16 30.00 Sterilized Control tests – 1,200
B17 30.04 No surfactant – 1,200

control test B17 in order to establish natural (background)
biodegradation efficiency.
All 17 microcosms, including two control tests, were kept
at 28 °C in a NOVATECH incubator. After 12 weeks, bio-
degradation process was interrupted and samples were
extracted. Humidity, microbial count, and final TPH-diesel
concentration were measured (procedures in NOM-021-
SEMARNAT-2000, Fernández et al. 2006, and U.S. EPA
1996, respectively).
2.5 Statistical comparison between soil washing
and biodegradation processes
Diesel elimination values in soil were analyzed by means of
a statistical approach in order to determine the distribution
and the statistical behavior of the TPH-diesel removal rate
variable in both soil washing and enhanced biodegradation
processes. R-Project Software, an open-source environment
for data manipulation, statistical analysis, and visualization,
was used for that purpose (R Development Core Team
2005).
3 Results and discussion
3.1 Soil characterization
The main characteristics of the soil are shown in Table 1.
There is a strong evidence of contamination caused by the
presence of TPH-diesel at a concentration of 32,100 mg/kg,
which is above the legal limit of 1,200 mg/kg for agricul-
tural soils in Mexico (SEMARNAT-SSA 2003). Regarding
physical properties, grain-size distribution shows that the
contaminated medium is basically a sandy soil (67 %) with
a fine fraction content of 20 %. Bulk density was 2.7 g/cm3,
total porosity, 41.6 %, and initial humidity about 7.6 %.
The adsorption coefficient (Kd) was estimated with batch
sorption isotherms experiments (Torres et al. 2003) by equil-
ibrating aqueous solutions of diesel with the soil from the
site. Figure 2 shows the results in terms of C* (which
represents the diesel concentration at equilibrium, in milli-
grams of TPH-diesel adsorbed per gram of soil) against Cw
(the diesel concentration dissolved into the water, in milli-
grams of TPH-diesel per liter of aqueous phase in equilib-
rium). The solid line represents Freundlich lineal
expression, where Kd is the slope of the line (Kd 0C*/Cw).
The experimental points were fitted to a straight line func-
tion with an acceptable Pearson coefficient of r00.914 (R2 0
0.837). This result shows that sorption processes in the
contaminated unsaturated zone are controlled by adsorption
linear isotherms with a Kd estimation of about 2.86 L/kg.
This value is linked to the easiness of desorbing diesel from
contaminated soils using either water or surfactant solutions.
Many hydrophobic compounds are removed from solu-
tion by sorption processes onto the soil or the aquifer matrix,
generating retarded motion of dissolved plumes into
groundwater. Kd can be used to estimate the retardation
factor (Rf) of diesel. This is perceived as a useful indicator
because few authors report Rf values for complex mixtures
such as diesel. Indeed, Rf values are usually reported for
158
14000
Sorbed Concentration, C* (mg/kg)
y = 2.8634x+2786
12000 2 acidic condition typical of felsic–rhyolitic volcanic soils. Re-
R = 0.8374
kd = C*/Cw
10000
8000
6000
4000
2000
0
0 2000 3000 4000
Aqueous phase concentration, Cw (mg/L)
Fig. 2 Adsorption isotherm for TPH-diesel in contaminated soil
single organic compounds, which are however uncommon
in field hydrocarbon spills.
Assuming that sorption transport in the saturated zone can
be adequately described by Kd, valid when the fraction of
organic carbon (foc) in soil is greater than 0.001 (Suthersan
2002), Rf can be assessed by Eq. 1. This expression is derived
from particular solutions of the advection–dispersion transport
equation (Fetter 1999):
ρb K d
Rf ¼ 1 þ
8
where Rf is the retardation factor, ρb soil bulk density, Kd
adsorption coefficient, and φ represents total porosity.
If the average linear groundwater velocity is vx, the
average velocity of the solute advective front, vc, is
given by vc 0 vx/Rf. Using Eq. 1, Rf (estimated in the
order of 12) can be used to asses groundwater velocity
of the polluted aquifer and compared to previous field
characterizations (Hernández-Espriú 2010; Hernández-
Espriú et al. 2012). This implies the assumption of
similar geological conditions between vadose-saturated
zones and a Fickian transport model (i.e., dispersive
mass flow rate is proportional to concentration gradi-
ent). Results suggest that diesel at site shows low mo-
bility in the subsurface (10 < Rf < 100) according to
Calabrase and Kostescki (1991) classification.
Literature showcases few reported Rf values for complex
mixtures such as diesel. For this reason, the reported value
can be used to asses solute advective transport processes in
other contaminated sites with similar conditions. For com-
parison reasons, Torres et al. (2003) reports Rf value of 2.9
in a contaminated sandy soil with diesel for a set of the
following conditions: fine fraction 0 7.9 %, φ047 %, foc 0
0.0096, ρs 01.52 g/cm3, and Kd 00.5 L/kg. Reported values
for single compounds are in the order of 1.47 and 3 for
benzene and antrazine, respectively, considering a foc of
0.01 (Calabrase and Kostescki 1991).
J Soils Sediments (2013) 13:152–165
On the other hand, soil chemical properties show a slightly
garding nutrient content, both nitrogen (391.43 mg/kg) and
soluble phosphorus (7.38 mg/kg) in soil are not sufficient to
support diesel biodegradation at an optimal C/N/P ratio of
100:15:1. Soils were conditioned by adding a solution of 2.1 g
of (NH4)2SO4 and distilled water in every microcosm. This
served the purpose of offsetting the nitrogen deficit. Natural
concentration of P was left untouched in order to evaluate
biodegradation and enhanced-biodegradation capability of the
system with an unusual nutrient ratio of 100:15:0.02. As
noted, metals in the studied soil have considerable concen-
trations. These include Co (34.73 mg/kg), Cu (102.83 mg/kg),
Pb (14.53 mg/kg), and Mg (190.12 mg/kg).
Microbial growth in the studied medium is notoriously
high, in the order of 2×1011 FCU/g soil. This is possibly due
to the humid tropical climate setting. Historical conditions
from 1965 to 2005 show that annual precipitation is about
1,100 mm/year and temperature is 21–24 °C. According to
Fahnestock (1998), a microbial growth of 103 FCU/g soil
(heterotrophic bacteria) is enough to support hydrocarbon
biodegradation. Iturbe et al. (2004) report bioremediation
results of an out-of-service oil distribution and storage sta-
tion. A 100-m3 biopile of soil at an initial TPH concentra-
tion of 4,600 mg/kg and heterotrophic bacteria count of
ð1Þ 1.8×108 FCU/g soil was operated during 66 days, reaching
a TPH removal of 85 %. In this sense, the soil studied in this
research showed an excellent microbiological activity, thus
an efficient background biodegradation removal rate was
expected.
3.2 Surfactant-enhanced washing process test
Figure 3 shows the results of the surfactant washing process
test in terms of percentage of TPH-diesel removal from soil.
Laboratory experiments suggest that soil-washing method-
ology is a feasible alternative to remediate the contaminated
vadose zone. As noted, control test (no surfactant) removed
40 % of the initial TPH-diesel concentration. This represents
the efficiency of soil washing remediation using only dis-
tilled water. Higher rates clearly suggest that TPH removal
is enhanced by the presence of surfactants. In general, ionic
surfactants showed removal rates above the control test of
about 78.51 % (Maranil LAB), 71.27 % (Texapon 40),
60.13 % (SDS), and 48.19 % (Surfacpol G).
In contrast, some ionic surfactants showed removal rates
below soil-washing background rate (40 %). These include
Polafix LO (18.23 %) and Surfacpol 14104 (17.19 %). In both
cases, surfactants were used at a fixed concentration of 0.5 %
(5 g/L). Results suggest that surfactants can enhance in some
cases the soil washing process. Therefore, treatability tests are
particularly important to underpin decisions and should be
included in engineering remediation projects. Khalladi et al.
J Soils Sediments (2013) 13:152–165 159

Fig. 3 TPH-diesel removal for 100

enhanced soil washing 90 Ionic
remediation process Non-ionic

TPH-diesel removal (%)

80 Zwitterionic
Natural gums
70
60 No surfactant
control test
50
40
30
20
10
0

SALEN SDS

LAB
MARANIL
LO
POLAFIX
14104
SURFACPOL

TEXAPONN-40

SURFACPOL G

BJ 35

MO8210
CANARCEL 20

TWEEN 80(1%)

TWEEN 80(0.5%)

SURFACPOL 203

POLAFIX CAPB

SEED GUM
MESQUITE
GUM
LOCUST BEAN

GUAR GUM

(2009) studied the diesel fuel removal from a soil column
using distilled water and surfactant solution (SDS). Soil com-
posed by a silt fraction of 94 %, porosity of 40 %, and a
density of 2.6 g/cm3 was artificially polluted by a diesel-oil
product and washed with distilled water and SDS at the critical
micelle concentration (CMC) of 8 mM or 400 mg/L. These
authors found a removal rate of 97 %, using n-alkanes as a
control parameter, after 4 h of treatment, superior to the
24.7 % removal value using only water.
The use of SDS as an enhancer in soil washing remedi-
ation processes has been documented in several works
(Fernandez and Luque 2000; Mulligan et al. 2001; Torres
et al. 2007). However, the specific performance of surfac-
tants related to soil washing processes and solubility of
hydrocarbons depends on many factors, such as nature and
quantity of surfactants, age of contamination, soil proper-
ties, and initial experimental setting (e.g., artificially pollut-
ed soil vs. actual contaminated soil). For this reason, it is
extremely important to assess site-specific conditions in
order to design effective remediation strategies.
For nonionic surfactants at a fixed concentration of
0.5 %, TPH-diesel removal rates were close to or below
the distilled water washing test. This corresponds to Brij 35
(41.78 %) or Canarcel 20 (15.24 %). Tween 80, tested at a
variable concentration of 0.5 % and 1 %, showed an effi-
ciency of 33.05 % and 32.10 %, respectively. This suggests
a slight or no effect at all over the removal rate due to
surfactant concentration. Surfacpol 203 was the only non-
ionic surfactant that showed a removal rate above the per-
formance of water in the removal of diesel fuel (about
52.69 %).
Recently, Villa et al. (2010) performed washing experi-
ments with a soil contaminated with pesticides and a soil
artificially polluted with diesel, using the nonionic surfac-
tant Triton X-100 (TX-100) as enhancer. They used concen-
trations equivalent to 3 CMC (2.1 g/L), 6 CMC (4.1 g/L),
and 12 CMC (8.3 g/L), reaching a diesel removal rate of
49 % and 87 % for 3 and 12 CMC, respectively. As noted,
WATER
DISTILLED
reported removal rates are in the same order of magnitude
than the TPH-diesel values estimated in this research.
On the other hand, natural gums showed interesting and
promising results. Guar gum and locust bean gum (LBG)
showed efficiencies of 54.38 % and 53.46 %, respectively.
These results show that natural gums at a low concentration
of 0.5 % improved the performance of water in the removal
of diesel fuel by about 15 %. TPH-diesel removal values
obtained for mesquite seed gum were below the distilled
water control test (24.28 %), suggesting that 0.1 % gum
concentration was too low to enhance remediation
sufficiently.
These results show that guar gum, part of the galacto-
mannans family, and LBG, a powder obtained by crushing
the endosperm of seeds from the fruit pod of the carob tree,
can be used as natural enhancers to improve efficiency of
conventional soil washing remediation processes. To our
knowledge, Torres et al. (2003) is the only work that reports
the application of guar and LBG as natural enhancers in soil
washing processes. These authors compared the perfor-
mance of guar and LBG with SDS in terms of their TPH
removal capabilities in a highly contaminated soil affected
by a crude spill (98,000 mg/kg of a mix of TPH-diesel,
TPH-gasoline, and heavier fractions). They reached removal
rates of 49.6 % and 47.7 % for guar and LBG, in compar-
ison with 36.3 % for SDS, all at the same surfactant con-
centration (0.5 %).
Surfactant-based vadose zone remediation enhance-
ment is related to aspects such as temperature, hydro-
philic–lipophilic balance, and surfactant’s dose. The
enhancement processes can take place at doses below
or above the CMC. At subcritical micellar concentra-
tions, the roll-up mechanism described by Deshpande et
al. (1999) controls the separation of contaminants and
soil particles. This is because surfactant monomers ac-
cumulate at soil–contaminant–water interfaces, increas-
ing the contact angle between geological media and
hydrophobic compounds.
160
At supracritical concentrations, solubilization is the most
effective process in soil-washing enhancement methodologies
because the pollutant is also partitioned into hydrophobic core
of surfactant micelles. In fact, it has been previously suggested
that the solubilization of hydrophobic compounds increases
linearly with surfactant’s CMC (Mulligan et al. 2001; Zheng
et al. 2002; Villa et al. 2010). In this research, surfactants were
used at supracritical concentrations to establish the solubiliza-
tion enhancement of diesel. For example, ionic and nonionic/
zwitterionic surfactants were tested at supracritical concentra-
tions, in the range of 3.43–12.5 to 50–153 times CMC,
respectively.
Considering a mixture of C6–C13 fractions and a diesel
solubility of less than 1 mg/L (McMillen et al. 2001), and
assuming that the difference between initial and final TPH-
diesel concentrations after the washing process in each test
corresponds to diesel concentration in aqueous phase, ex-
perimental results suggest that diesel solubility improves
between 8,000 and 25,000 times. These values are roughly
consistent to those reported by other authors. Deshpande et
al. (1999), for instance, quotes a 10- to 100-fold improve-
ment, while Torres et al. (2003) mention 8,000 to 17,600.
Moreover, diesel solubility enhancement and pollutant re-
moval rate in the studied soil indicates a large amount of
TPH elimination within only 24 h of continuous washing.
This is a particularly significant finding since several wash-
ing stages can be applied at both laboratory and field scales.
Iturbe et al. (2004) report remediation results of a soil
washing process at field level. Approximately 1,540 m3 of a
soil contaminated with gasoline and diesel, at a TPH con-
centration of 3,073–17,328 mg/kg, were washed using water
and a nonionic surfactant (Canarcel TW80) in three washing
stages. After the remediation process, an exponential TPH
removal function was characterized, in the form of TPH
removal 0 aebn, where a and b are constants and n is the
number of washing stages.
Unitary TPH removal efficiencies, a parameter defined
by Iturbe et al. (2004) as the amount (in grams) of TPH
removed per gram of employed surfactant, is particularly
useful in assessing which surfactant yielded the maximum
100
Unitary efficiency (gTPH/g surf)
90
80
70 y = 0.7151e 0.0275x
2
60 R = 0.8972
50
40
30
20
10
0 yielded the highest TPH removal rate of all natural gums
0 10 20 30 40
TPH-diesel removal (%)
Fig. 4 Unitary removal efficiency (g TPH/g surfactant) as a function
of TPH-diesel removal
J Soils Sediments (2013) 13:152–165
diesel removal per gram of surfactant used. As shown in
Fig. 4, unitary efficiencies range between 0.98 and 5.05 g
TPH/g surfactant. These figures correspond to Brij 35 and
Maranil LAB surfactants, respectively. Remarkably, natural
gums showed the highest unitary efficiencies of about 3.44
(mesquite seed gum), 3.50 (LBG), and 3.87 (guar gum) g
TPH/g gum. In general, the median value of each surfac-
tant’s nature group was 3.6 g TPH/g surfactant for natural
gums, 3.1 g TPH/g surfactant for ionic surfactants, and
1.96 g TPH/g surfactant for nonionic surfactants. In this
sense, unitary values suggest that natural gums provide a
cost-effective solution as enhancement products for improv-
ing soil-washing methodologies.
Furthermore, TPH-diesel removal rate and unitary effi-
ciency fit an exponential function of the type TPH removal
rate (%) 0 0.7151e0.027*UE (gTPH/gsurf.), where UE is the
unitary efficiency (Pearson coefficient, r00.94; R2 00.89).
3.3 Surfactant-enhanced biodegradation test
Figure 5 shows the experimental results of the surfactant-
enhanced biodegradation test expressed as a percentage of
TPH-diesel removal from soil. The microcosm B16, where
sterilization was performed, yielded a 2.76 % TPH removal.
This suggests that abiotic removal is very low compared to
biological TPH degradation. As noted, the non-surfactant
microcosm test (B17) removed 59 % of the initial TPH-
diesel concentration. This represents a high background
biodegradation rate controlled by an important microbial
growth activity (2×1011 FCU/g soil). Rates in excess of
background removal clearly suggest that the presence of
natural gums and surfactants enhances the biodegradation
process. Besides, it is important to remember that maximum
potential removal was not reached because tests were arbi-
trarily limited to 12 weeks.
Nonionic surfactant Brij 35, performed below back-
ground biodegradation rate at variable doses of 2 (B01),
20 (B02), and 200 mg/kg (B03), yielded TPH-diesel remov-
al values of 17.25 %, 42.86 %, and 55.34 %, respectively. In
contrast, Maranil LAB, an ionic surfactant, showed removal
rates of 70.59 % and 90.51 %, which was the highest value
of all microcosms, for 2 (B04) and 20 mg/kg (B05), respec-
tively. Zwitterionic surfactant Polafix CAPB showed a TPH
removal rate slightly above control test, at variable doses of
2 (B07) and 20 (B08) mg/kg (62.48 % and 66 %). However,
diesel reduction was inhibited at a maximum surfactant
concentration of 200 mg/kg (B09).
Natural gums showed remarkable results. Guar gum
50 60 70 80 90 100 (82 %) with a very low concentration of only 2 mg/kg
(B10). This value represents a diesel elimination enhance-
ment of 23 %. Nevertheless, removal rate was reduced as
guar’s gum concentration was increased, as shown in
J Soils Sediments (2013) 13:152–165 161

Fig. 5 TPH-diesel removal for Non-ionic

100
enhanced biodegradation Ionic
Zwitterionic
remediation process 90 Natural gums

TPH-diesel removal (%)

80
Sterilized test
70 No surfactant
control test
60
50
40
30
20
10
0

B01

B02

B03

B04

B05

B07

B08

B09

B10

B12

B13

B14

B15

B16

B17
B11
Microcosm

microcosms B11 and B12, where TPH-diesel removal val- g soil below the initial microbiological activity (1011 CFU/g
ues of 76.53 % and 67.47 % were measured using gum’s soil) in the order of 108–1011 CFU/g soil. This becomes
doses of 20 and 200 mg/kg, respectively. These results particularly clear for microcosms B10 (guar gum at 2 mg/
suggest that guar gum can be used as a natural enhancer to kg), B11 (guar gum at 20 mg/kg), and B12 (guar gum at
improve background diesel biodegradation processes in 200 mg/kg), which showed microbial growths of 4.671×
soils. In contrast, Torres et al. (2004) report laboratory 108, 1.32×1010, and 3.91×108 CFU/g soil, respectively. As
biodegradation results where guar gum was tested as natural noted, the lower microbial growth measured in microcosm
enhancer using three different doses (2, 20, and 200 mg/kg) B12 (where the maximum guar gum dose was applied)
in a contaminated sandy soil (initial TPH-diesel concentra- suggests that the 200 mg/kg dose became slightly toxic for
tion of 3970 mg/kg) from an old storage and distribution indigenous microorganisms.
station of northern Mexico. After 8 weeks of biodegradation On the other hand, TPH-diesel removal as a function of
process, final TPH-diesel concentration value was, in all surfactant dose is shown in Fig. 7. Although the trend is not
three cases, lower than the no-surfactant control test, with unequivocally clear, it is possible to establish that nonionic
diesel removal rates below 10 %. However, as noted in this surfactants inhibit the background diesel biodegradation
research, biodegradation rate was lower as surfactant dose process regardless of their concentration. As shown, there
increased for this particular gum. is direct proportionality between surfactant dose and diesel
LBG, evaluated in microcosms B13, B14, and B15, elimination in the case of ionic surfactants. Conversely, guar
showed results above the control test, yielding TPH- gum showed inverse proportionality between these two
removal values of 53.16 %, 81 %, and 85.30 % for doses variables. Several reasons explain why, the main ones being
of 2, 20, and 200 mg/kg, respectively. However, LBG surfactant chemical family, soil characteristics, and the fact
showed an opposite behavior to guar gum regarding diesel that numerous properties affect TPH-diesel remediation be-
removal and dose relationship. This suggests that guar gum sides the applied dose.
inhibited TPH-diesel biodegradation at specific concentra- Shin et al. (2004) studied phenanthrene solubilization and
tions. At higher doses, even natural products can inhibit biodegradation with a rhamnolipid as a function of pH
TPH removal (Torres et al. 2004). This aspect can be seen solution with a fixed concentration of 240 ppm. Batch
in Fig. 6 where final biomass growth was plotted as a
function of surfactant dose. All microcosms showed CFU/ 100
90
1.E+12 80
TPH-diesel removal (%)

70
1.E+09
60
50
FCU/g soil

Brij 35 (NI)
1.E+06 Maranil LAB (I) 40
Polafix CAPB (Z) Brij 35 (NI)
30
Guar gum (N) Maranil LAB (I)
1.E+03 Locust bean gum (N) Polafix CAPB (Z)
20
Guar gum (N)
Initial FCU/g soil Locust bean gum (N)
10
1.E+00 Initial FCU/g soil
10 1000 0
1 100 1 10 100 1000
Surfactant dose (mg/kg) Surfactant dose (mg/kg)

Fig. 6 Microbial growth as a function of surfactant dose. I ionic, NI Fig. 7 TPH-diesel removal as a function of surfactant dose. I ionic, NI
nonionic, Z zwitterionic, N natural gum nonionic, Z zwitterionic, N natural gum
162 J Soils Sediments (2013) 13:152–165

Fig. 8 TPH-diesel removal rate

90th percentile
comparison between enhanced 75th percentile

100
soil washing and biodegradation median
processes. (a), (b), and (c) show 25th percentile
surfactant dose of 2, 20, and 10th percentile
200 mg/kg, respectively Maranil LAB
Polafix CAPB

80
Guar gum
Locust bean gum
Outlier

TPH−diesel removal (%)

No surfactant
control test

60

2 mg/kg
40

20 mg/kg

200 mg/kg
20

a b c
0

Surfactant enhanced Surfactant enhanced

biodegradation test soil-washing test

phenanthrene experiments were performed in a pH range of
4 to 8. The highest solubilities and biodegradation rates with
the biosurfactant were detected around a pH of 4.5–5.5. In
this context, Torres et al. (2005) assess the combined effect of
temperature, surfactant’s hydrophilic–lipophilic balance
(HLB), and dose over TPH-diesel removal in an aged soil.
Their results indicated that the parameter that mostly affected
biodegradation process was temperature, followed by surfac-
tant’s HLB value. Somewhat surprisingly, surfactant dose
proved to be the least important parameter.
Factors involved in surfactant-assisted biodegradation and
the comprehensive understanding of individual surfactants, as
well as the implications of combining different types of sur-
factants and mixing them with compounds of different nature
(e.g., salts), are the object of current scientific debates (Dal-
Heui et al. 2008; Guimaraes-Martins et al. 2009; Wen-Bin et
al. 2009; Seok-Whan et al. 2010; Sivaraman et al. 2010). The
amplitude of this field suggests that there is still plenty of
room for improvement in terms of understanding these aspects
of surfactant-based remediation.
slightly and strongly asymmetrical for biodegradation and
soil washing processes, respectively. For these skewed dis-
tributions, a log transformation is common to better visualize
the variable in various types of models (Rossiter 2011). Log-
transformation distributions are shown in Fig. 8.
First, enhanced biodegradation process (see Fig. 9a)
exhibits a left-skewed distribution because mean TPH re-
moval value (63.85 %) is lower than the median rate
(66.75 %). This suggests that most of the TPH removal
values are above the background rate (no surfactant). The
highest frequency (10) corresponds to the higher TPH-diesel
removal class, ranging from 101.8 to 102 or 63–100 %
(79.43 % in average). Also, a frequency of 4 corresponds
to 101.6–101.8 TPH removal rates, or 40–63 %. These results
imply that enhanced biodegradation provides a feasible al-
ternative for environmental treatment of the vadose zone.
10 10

8
a 8
b
3.4 Statistical comparison between soil washing
Frequency

6 6
and biodegradation processes 4 4

2 2
Diesel reduction values were analyzed from a statistical
0 0
perspective. In order to determine the distribution and the 1.0 1.2 1.4 1.6 1.8 2.0 1.0 1.2 1.4 1.6 1.8 2.0
statistical behavior of the variable “TPH-diesel removal Log-TPH Removal Log-TPH Removal

rate” in both soil washing and enhanced biodegradation Fig. 9 Histograms of surfactant-enhanced biodegradation test (a) and
processes, a frequency histogram of each process was per- surfactant-enhanced washing process test (b), showing the distribution
formed. Distribution of TPH-diesel removal response was of the variable Log10(TPH-diesel removal)
J Soils Sediments (2013) 13:152–165
In contrast, enhanced washing process test (see Fig. 9b)
exhibits a slightly right-skewed distribution (mean higher than
median value, or 43.10 %>41.78 %). This means that practi-
cally half of the TPH removal distribution is very close to the
performance of water-based washing (no surfactant). Log-
transformation distribution shows a bimodal behavior with
frequencies of 7 and 3, corresponding to TPH-diesel removal
rates of 39.8–63 % (101.6–101.8) and 15.8–25 %, respectively.
Simultaneous comparison of both processes is shown in
Fig. 8 box plot. Biodegradation box plot also shows TPH-
diesel removal rates for specific surfactants (Maranil LAB
and Polafix CAPB) and gums (guar and LBG) at each tested
dose (2, 20, and 200 mg/kg). Regarding enhanced biodeg-
radation process, 10th and 90th percentiles correspond to
40.26 % and 83.64 % removal rates, respectively, while
median is well above the no-surfactant rate (66.75 %>
59 %). These results suggest that more than half of the
diesel deduction distribution exceeded biodegradation back-
ground process by the presence of surfactants. Specifically,
guar gum showed excellent performance because 82 % of
TPH-diesel removal was achieved at a very low concentra-
tion of only 2 mg/kg. In general, this is the ideal scenario in
enhanced-remediation strategies applying surfactants: max-
imize pollutant removal using the minimum amount of
product. For this reason, guar gum might represent a very
cost-effective solution for biodegradation enhancement pro-
cesses in similar conditions. It is, however, acknowledged
that further research is necessary to confirm this conclusion.
Reported surfactant efficiency can be compared to
other experiences. For example, Lai et al. (2009) eval-
uate oil removal capability of several surfactants for oil-
contaminated soils collected from a heavy oil-polluted
site. By using a concentration of 2,000 mg/kg, or 0.2
mass% of rhamnolipids, surfactin, Tween 80, and Triton
X-100, removal efficiency was 23 %, 14 %, 6 %, and
4 %, or even up to 63 %, 62 %, 40 %, and 35 %, using
an initial TPH concentration in soil of 3,000 and
9,000 mg/kg, respectively. As can be seen, the surfac-
tant concentration employed by these authors is three
orders of magnitude higher than the concentration of
guar gum used in this research, which yielded 82 %
of oil removal, at an initial TPH-diesel concentration in
soil of 32,000 mg/kg.
Soil washing box plot shows lower performance for the
surfactants used in both processes (Maranil LAB, Polafix
CAPB, guar gum, and LBG). The 10th and 90th percentiles
correspond to TPH-diesel removal values of 20 % and
66.8 %, respectively. Median value is very close to the no-
surfactant control test (in the order of 41 %). As shown, guar
gum performance yielded a 53 % diesel fuel removal, which
is exactly the 75th percentile value of the distribution.
However, in this case, guar gum was used at a much higher
concentration (5,000 mg/L).
163
4 Conclusions
This work demonstrated the applicability of natural gums as
soil remediation enhancers in diesel-contaminated systems.
Locust bean, guar, and mesquite seed gums were assessed in
terms of their TPH-diesel removal capability in highly con-
taminated soil samples (initial concentration of 32,000 mg/
kg) from a polluted site of the western part of Trans-
Mexican Volcanic Belt, Mexico.
The following major conclusions can be drawn from this
research. In the case of soil washing experiments, ionic
surfactants significantly enhanced the TPH-diesel removal.
Maranil LAB, Texapon 40, SDS, and Surfacpol G showed
removal rates of 78.51 %, 71.27 %, 60.13 %, and 48.19 %,
respectively, all above the removal value of the no-
surfactant control test (40 %). In contrast, removal rates
for nonionic surfactants, such as Brij 35 or Carnacel 20,
were close or below the distilled water control test.
Natural gums have shown interesting and promising
results. Addition of guar and LBG significantly increases
diesel solubility reaching removal values of 54.38 % and
53.46 %, which means an enhancement in the order of 14 %.
Remarkably, natural gums showed the highest unitary effi-
ciencies: 3.44 (mesquite gum), 3.50 (LBG), and 3.87 (guar
gum) g TPH removed/g gum.
On the other hand, no-surfactant microcosm test removed
59 % of the initial TPH concentration which represents a high
background biodegradation rate. This is attributed to microbi-
al activity (2×1011 FCU/g soil). In this sense, biodegradation
experiment confirmed the effectiveness of natural gums as
biodegradation enhancers in diesel-contaminated soils. Spe-
cifically, guar gum showed an excellent performance. An
82 % TPH-diesel removal rate was achieved for a very low
gum concentration (2 ppm); in this particular context, reported
surfactant concentrations to assist biodegradation are, in gen-
eral, higher. This suggests that guar gum might represent a
cost-effective alternative for biodegradation enhancement
processes.
References
Althoff K, Mundt M, Eisentraeger A, Dott W, Hollender J (2001)
Microcosms-experiments to assess the potential for natural atten-
uation of contaminated groundwater. Water Res 35(3):720–728
American Society for Testing and Materials, ASTM, (2000) Standard
Practice for Soil Exploration and Sampling by Auger Borings.
ASTM D1452-09
Arrar J, Chekir N, Bentahar F (2007) Treatment of diesel fuel contam-
inated soil in jet-fluidized bed. Biochem Eng J 37:131–138
Blake GR, Hartage KH (1986) Bulk Density. In: Klute A (ed) Methods
of soil analysis. Part I. Physical and mineralogical methods,
Agronomy 9, 2nd edn. American Society of Agronomy, Madison,
pp 363–375
164
Bray RH, Kurtz LT (1945) Determination of total, organic and avail-
able form of phosphorus in soil. Soil Sci 59:360–361
Calabrase EJ, Kostecki PT (1991) Hydrocarbon contaminated soils.
Lewis, Boca Raton
Chaplin M (2003) Guar gum. www.sbu.ac.ik/water/hygua.html
Conte P, Agretto A, Spaccini R, Piccolo A (2005) Soil remediation:
humic acids as natural surfactants in the washings of highly
contaminated soils. Environ Pollut 135:515–522
Dakia PA, Blecker C, Robert C, Wathelet B, Paquot M (2008) Com-
position and physicochemical properties of locust bean gum
extracted from whole seeds by acid or water dehulling pre-
treatment. Food Hydrocolloids 22:807–818
Dal-Heui L, Ho-Wan C, Chul K (2008) Mixing effect of NaCl and
surfactant on the remediation of TCB contaminated soil. Geosci J
12(1):63–68
Danielson RE, Sutherland PL (1986) Porosity. In: Klute A (ed) Meth-
ods of soil analysis. Part I. Physical and mineralogical methods,
Agronomy 9, 2nd edn. American Society of Agronomy, Madison,
pp 443–461
Desphande S, Shiau BJ, Wade D, Sabatini DA, Harwell JH (1999)
Surfactant selection for enhancing ex situ soil washing. Water Res
33(2):351–360
Fahnestock FM (1998) Biopile design: operation and maintenance hand-
book for treating hydrocarbon-contaminated soils. Battelle, EUA
Fernández Linares LC, Rojas Avelizapa NG, Roldán Carrillo TG,
Ramírez Islas ME, Zegarra Martínez HG, Uribe Hernández R,
RJ RÁ, Flores Hernández D, Arce Ortega JM (2006) Manual de
técnicas de análisis de suelos aplicadas a la remediación de sitios
contaminados. Instituto Mexicano del Petróleo, Secretaría de
Medio Ambiente y Recursos Naturales, Instituto Nacional de
Ecología, México. ISBN 968-489-039-7
Fernández-Pérez V, Luque de Castro MD (2000) Micelle formation for
improvement of continuous subcritical water extraction of poly-
cyclic aromatic hydrocarbons in soil prior to high-performance
liquid chromatography-fluorescence detection. J Chromatogr A
902(2):357–367
Fetter CW (1999) Contaminant hydrogeology. Prentice-Hall, New
Jersey
Goi A, Trapido M, Kulik N, Palmorth MRT, Tuhnkanen T (2006)
Ozonation. Sci Eng 28(1):37–46
Guimaraes-Martins V, Juliano-Kalil S, Vieria-Costa JA (2009) In situ
bioremediation using biosurfactant produced by solid state fer-
mentation. World J Microbiol Biotechnol 25:843–851
Hernandez-Espriú A (2010) Estrategia integral de remediación en un
sitio contaminado por hidrocarburos: simulación de los procesos
de descontaminación de suelos y acuíferos con modelación mate-
mática y análisis en laboratorio. PhD thesis, Universidad Com-
plutense de Madrid
Hernández-Espriú A, Martínez-Santos P, Sánchez-León E, Marín LE
(2012) Free-product plume distribution and recovery modeling
prediction in a diesel-contaminated volcanic aquifer. Phys Chem
Earth 37–39:43–51
Iturbe R, Flores C, Chávez C, Bautista G, Torres LG (2004) Remedi-
ation of contaminated soil using soil washing and biopile meth-
odology at a field level. J Soils Sediments 4(2):115–122
Iturbe R, Flores C, Castro A, Torres LG (2007) Sub-soil contamination
due to oil spills in six oil-pipeline pumping stations in northern
Mexico. Chemosphere 68:893–906
Juárez-Badillo E, Rico A (1973) Mecánica de Suelos, Tomo 1: Funda-
mentos de la mecánica de suelos, Limusa
Khalladi R, Benhabiles O, Bentahar F, Moulai-Mostefa N (2009)
Surfactant remediation of diesel fuel polluted soil. J Hazard Mater
164:1179–1184
Klute A (1986) Water retention: laboratory methods. In: Klute A (ed)
Methods of soil analysis. Part 1. Physical and mineralogical methods,
2nd edn. American Society of Agronomy, Madison, pp 635–662
J Soils Sediments (2013) 13:152–165
Knop A, Cruz RC, Heineck KS, Consoli NC (2005) Solidification/
stabilization of a residual soil contaminated by diesel oil. Proceed-
ings of the International Conference on Deep Mixing Best Prac-
tice and Recent Advances 1.2:363–367
Lai C, Huanga Y, Wei Y, Chang J (2009) Biosurfactant-enhanced
removal of total petroleum hydrocarbons from contaminated soil.
J Hazard Mater 167:609–614
Liu PWG, Whang LM, Yang MC, Cheng SS (2008) Biodegradation of
diesel-contaminated soil: a soil column study. J Chin Inst Chem
Eng 39(5):419–428
López J, Iturbe R, Torres LG (2004) Washing of soil contaminated with
PAH’s and heavy petroleum fractions using two anionic and one
ionic surfactant: effect of salt addition. J Environ Sci Health, Part
A: Toxic/Hazard Subst Environ Eng 39(9):2293–2306
Mao L, Yue Q (2010) Remediation of diesel-contaminated soil by
bioventing and composting technology. International Conference
on Challenges in Environmental Science and Computer
Engineering
Mariano AP, Geraldes-Kataoka APA, de Angelis DF (2007) Laborato-
ry study on the bioremediation of diesel oil contaminated soil
from a petrol station. Braz J Microbiol 38:346–353
McMillen S, Rhodes I, Nakles DV, Sweeney RE (2001) Application of
the Total Petroleum Hydrocarbon Criteria Working Group
(TPHCWG) methodology to crude oils and gas condensates. In:
McMillen SJ, Magaw RI, Carovillano RL (eds) Risk-based
decision-making for assessing petroleum impacts at exploration
and production sites. US Department of Energy, Washington DC
Mulligan CN, Yong RN, Gibbs BF (2001) Surfactant-enhanced reme-
diation of contaminated soil: a review. Eng Geol 60:371–380
Orozco-Villafuerte J, Cruz-Sosa F, Ponce-Alquicira E, Vernon-Carter
EJ (2003) Mesquite gum: fractionation and characterization of the
gum exuded from Prosopis laevigata obtained from plant tissue
culture and from wild trees. Carbohydr Polym 54:327–333
Page M, Page CL (2002) Electroremediation of contaminated soils. J
Environ Eng 128(3):208–216
R Development Core Team (2005) R: A language and environment for
statistical computing. R Foundation for Statistical Computing,
Vienna. ISBN 3-900051-07-0
Román-Guerrero A, Orozco-Villafuerte J, Pérez-Orozco JP, Cruz-Sosa F,
Jiménez-Alvarado R, Vernon-Carter EJ (2009) Application and eval-
uation of mesquite gum and its fractions as interfacial film formers
and emulsifiers of orange peel-oil. Food Hydrocolloids 23:708–713
Rossiter DG (2011) A minimal introduction to geostatistics with R/
gstat. University of Twente, Faculty of Geo-Information Science
& Earth Observation (ITC)
SEMARNAT (2000) Norma Oficial Mexicana NOM-021-SEMARNAT
-2000, Que establece las especificaciones de fertilidad, salinidad y
clasificación de suelos. Estudios, muestreo y análisis
SEMARNAT-SSA (2003) Norma Oficial Mexicana NOM-138-
SEMARNAT/SSA1-2003, Que establece los límites máximos
permisibles de hidrocarburos en suelos y las especificaciones para
su caracterización y remediación
SEMARNAT-SSA (2004) Norma Oficial Mexicana NOM-147-
SEMARNAT/SSA1-2004. Criterios para determinar las concen-
traciones de remediación de suelos contaminados por arsénico,
bario, berilio, cadmio, cromo hexavalente, mercurio, niquel, plata,
plomo, selenio, talio y/o vanadio
Seok-Whan K, Young-Bum K, Jae-Dong S, Eun-Ki K (2010) Enhanced
biodegradation of hydrocarbons in soil by microbial biosurfactant.
Sophorolipid Appl Biochem Biotechnol 160(3):780–790
Sharma A, Rehman MB (2009) Laboratory scale bioremediation of
diesel hydrocarbon in soil by indigenous bacterial consortium.
Indian J Exp Biol 47:766–769
Shin KH, Kim KW, Seagren EA (2004) Combined effects of pH and
biosurfactant addition on solubilization and biodegradation of
phenanthrene. Appl Microbiol Biotechnol 65:336–343
J Soils Sediments (2013) 13:152–165
Sivaraman C, Anasuya G, Srikanth M (2010) Biodegradation of hydro-
carbons in the presence of cyclodextrins. World J Microbiol Bio-
technol 26:227–232
Soeder CJ, Papaderos A, Kleespies M, Kneifel H, Haegel FH, Webb L
(1996) Influence of phytogenic surfactants (quillaya saponins and
soya lecithin) on bio-elimination of phenanthrene and fluoran-
thene by three bacteria. Appl Microbiol Biotechnol 44:654–659
Suthersan S (2002) Natural and enhanced remediation systems (Ger-
aghty and Miller Environmental Science and Engineering Series).
CRC, Boca Raton
Tiehm A, Schulze S (2003) Intrinsic aromatic hydrocarbon biodegra-
dation for groundwater remediation. Oil Gas Sci Technol 58
(4):449–462
Torres LG, Orantes JL, Iturbe R (2003) Critical micellar concentrations
for three surfactants and their diesel-removal efficiencies in
petroleum-contaminated soils. Environ Geosci 10(1):28–36
Torres LG, Rojas N, Iturbe R (2004) Use of two-surfactants mixtures to
attain specific HLB values for assisted TPH-diesel biodegrada-
tion. J Environ Sci 16(6):950–956
Torres LG, Rojas N, Bautista G, Iturbe R (2005) Effect of temperature,
and surfactant’s HLB and dose over the TPH-diesel biodegrada-
tion process in aged soils. Process Biochem 40:3296–3302
Torres LG, Zavala P, Beltrán M, Vaca M, Iturbe R (2007) Combination
of natural gums and synthetic surfactants for washing of a soil
highly contaminated with crude. Environ Geosci 14(1):49–58
U.S. Environmental Protection Agency (1995) How to evaluate alternative
cleanup technologies for underground storage tank sites. A guide for
corrective action plan reviewers. EPA 510-B-95-007. Washington, DC
U.S. Environmental Protection Agency (1996) Soxhlet extraction. EPA
3540C
Urum K, Pekdemir T (2004) Evaluation of biosurfactants for crude oil
contaminated soil washing. Chemosphere 57:1139–1150
165
Villa RD, Trovó AG, Pupo Nogueira RF (2010) Soil remediation using
a coupled process: soil washing with surfactant followed by
photo-Fenton oxidation. J Hazard Mater 174:770–775
Vreysen S, Maes A (2005) Remediation of a diesel contaminated,
sandy-loam soil using low concentrated surfactant solutions. J
Soils Sediments 4:240–244
Walkley A, Black A (1934) An examination of the Degtjareff method
for determining organic carbon in soils: effect of variations in
digestion conditions and of inorganic soil constituents. Soil Sci
63:251–263
Wen-Bin X, Xin L, Hui G, Bao-Rong H, Hui-Zhi Z, Yun-Guo L, Guang-
Ming Z, Ting F (2009) Influence factors analysis of removing heavy
metals from multiple metal-contaminated soils with different extrac-
tants. J Cent South Univ Technol 16:0108–0111
Whang L, Liu PWG, Ma C, Cheng S (2008) Application of biosurfac-
tants, rhamnolipid, and surfactin, for enhanced biodegradation of
diesel-contaminated water and soil. J Hazard Mater 151:155–163
Xu P, Achari G, Mahmoud M, Joshi RC (2006) Application of Fen-
ton’s reagent to remediate diesel contaminated soils. Pract Period
Hazard Toxic Radioact Waste Manage 10(1):19
Zhang M, Zhu L (2010) Effect of SDBS–Tween 80 mixed surfactants
on the distribution of polycyclic aromatic hydrocarbons in soil–
water system. J Soils Sediments 10:1123–1130
Zheng Z, Obbard JP (2002) Evaluation of an elevated non-ionic
surfactant critical micelle concentration in a soil/aqueous system.
Water Res 36:2667–2672
Zhou W, Zhu L (2007) Efficiency of surfactant-enhanced desorption
for contaminated soils depending on the component character-
istics of soil–surfactant PAHs system. Environ Pollut 147:66–73
Zhou W, Zhu L (2008) Influence of surfactant sorption on the removal
of phenanthrene from contaminated soils. Environ Pollut 152:99–
105
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.